JP3248424B2 - Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg - Google Patents
Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepregInfo
- Publication number
- JP3248424B2 JP3248424B2 JP12756696A JP12756696A JP3248424B2 JP 3248424 B2 JP3248424 B2 JP 3248424B2 JP 12756696 A JP12756696 A JP 12756696A JP 12756696 A JP12756696 A JP 12756696A JP 3248424 B2 JP3248424 B2 JP 3248424B2
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene oxide
- epoxy resin
- prepreg
- modified polyphenylene
- ppo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
- Polyethers (AREA)
- Epoxy Resins (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、変成ポリフェニレ
ンオキサイドの製法、この製法による変成ポリフェニレ
ンオキサイドを用いたエポキシ樹脂組成物、この組成物
を用いたプリプレグ、及びこのプリプレグを用いた積層
板に関し、半導体等の電子部品を搭載する回路板に加工
される積層板に有用なものである。The present invention relates to a method for producing a modified polyphenylene oxide, an epoxy resin composition using the modified polyphenylene oxide obtained by the method, a prepreg using the composition, and a laminate using the prepreg. It is useful for a laminate processed into a circuit board on which electronic components such as the above are mounted.
【0002】[0002]
【従来の技術】エポキシ樹脂、エポキシ樹脂の硬化剤、
及びポリフェニレンオキサイド(以下、PPOと記す)
の硬化物がガラスクロスと一体となった積層板は、19
70年にはすでに知られている。この種のポリフェニレ
ンオキサイド−エポキシ樹脂系の熱硬化型樹脂の硬化物
から成る積層板は、優れた高周波特性、特に、誘電率、
誘電正接の特性を備えている点で、衛星通信波領域で使
用されるXバンド(10GHz)領域に好適である。2. Description of the Related Art Epoxy resin, epoxy resin curing agent,
And polyphenylene oxide (hereinafter referred to as PPO)
The laminated board in which the cured product of
It has been known for 70 years. A laminate made of a cured product of this type of polyphenylene oxide-epoxy resin-based thermosetting resin has excellent high-frequency characteristics, in particular, dielectric constant,
Since it has a dielectric loss tangent characteristic, it is suitable for the X band (10 GHz) region used in the satellite communication wave region.
【0003】ところが、高分子量のPPOは、ガラス転
移温度が高いことに関連して溶融粘度が高ために、この
種のPPOを含有したプリプレグを加熱加圧する成形加
工性が悪い。[0003] However, high-molecular-weight PPO has a high melt viscosity associated with a high glass transition temperature, and therefore has poor molding processability for heating and pressing a prepreg containing this type of PPO.
【0004】そこで、他の樹脂とのブレンドにより改善
する解決手段が模索されているが、PPOは相溶性が乏
しく、機械的強度に難点があり、この問題解決のために
相溶化剤として両者のポリマーのグラフト、またはブロ
ックの共重合体の使用が考えられる。これらの共重合体
は無変成のPPOの末端に結合したフェノール性水酸基
を他のポリマー中の官能基と反応させることによって生
成される。これらの他のポリマーで変成したPPOとし
ては、たとえば特公昭53−12557号公報によって
固有粘度0.6以下のPPOとエピクロルヒドリンを触
媒の存在下で反応させることによって末端をエポキシ化
した変成PPOを製造する方法、特開平4−26142
6号によって末端をエポキシ化した変成PPOにポリカ
ルボン酸を反応させることによって末端カルボン酸変成
PPOを製造する方法、特開平4−80231号公報に
よって末端をエポキシ化した変成PPOにポリアミン化
合物を反応させることによって末端アミノ化変成PPO
を製造する方法が知られている。[0004] In order to solve this problem, PPO has poor compatibility and has poor mechanical strength. However, in order to solve this problem, both are used as compatibilizers. Use of polymer grafts or block copolymers is contemplated. These copolymers are formed by reacting unmodified PPO-terminated phenolic hydroxyl groups with functional groups in other polymers. Examples of the PPO modified with these other polymers include a modified PPO having an epoxidized terminal by reacting PPO having an intrinsic viscosity of 0.6 or less with epichlorohydrin in the presence of a catalyst as disclosed in Japanese Patent Publication No. 53-12557. Japanese Patent Application Laid-Open No. 4-26142
No. 6, a method for producing a modified carboxylic acid terminal PPO by reacting a modified PPO having an epoxidized terminal with a polycarboxylic acid, and a method of reacting a modified PPO having an epoxidized terminal with a polyamine compound according to JP-A-4-80231. The terminal aminated modified PPO
A method for producing is known.
【0005】これらの製法で得られた変成PPOは、前
述の如く溶融粘度が高く、その結果積層板の銅箔のピー
リング強度が弱く、プリプレグの層間にメッキが染み込
む現象が起き、また樹脂の含浸性が悪いことに起因する
半田耐熱性が低い問題がある。The modified PPO obtained by these methods has a high melt viscosity as described above, and as a result, the peeling strength of the copper foil of the laminated board is weak, so that a phenomenon occurs in which plating infiltrates between the layers of the prepreg, and the resin impregnation occurs. There is a problem of low solder heat resistance due to poor solderability.
【0006】[0006]
【発明が解決しようとする課題】本発明は上記の事情に
鑑みてなされたもので、その目的とするところは、金属
箔の引き剥がし強度、半田耐熱性、メッキ染み込み性並
びに高周波特性の指標である誘電率、誘電正接特性に優
れた積層板の製造に有用なエポキシ樹脂組成物を構成す
る変成ポリフェニレンオキサイドの製法、変成ポリフェ
ニレンオキサイドを用いたエポキシ樹脂組成物、この組
成物を用いたプリプレグ、及びこのプリプレグを用いた
積層板を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to measure the peeling strength of metal foil, solder heat resistance, plating penetration, and high-frequency characteristics. A certain dielectric constant, a method for producing a modified polyphenylene oxide constituting an epoxy resin composition useful for producing a laminate having excellent dielectric loss tangent characteristics, an epoxy resin composition using the modified polyphenylene oxide, a prepreg using this composition, and An object of the present invention is to provide a laminate using the prepreg.
【0007】[0007]
【課題を解決するための手段】本発明の請求項1乃至請
求項3に係る変性ポリフェニレンオキサイドの製法は、
数平均分子量が10000〜30000の高分子量のポ
リフェニレンオキサイドをポリフェノール性化合物とラ
ジカル開始剤の存在下で再分配反応させて得られた数平
均分子量が1000〜3000のフェノール変性ポリフ
ェニレンオキサイド、及びエピクロルヒドリンとを反応
させるもので、末端にエポキシ基を導入した低分子量の
変成ポリフェニレンオキサイドが生成する。According to a first aspect of the present invention, there is provided a method for producing a modified polyphenylene oxide, comprising the steps of:
A number average molecular weight of 10,000 to 30,000 high molecular weight polyphenylene oxide and a polyphenol compound and a number average molecular weight obtained by performing a redistribution reaction in the presence of a radical initiator, a phenol-modified polyphenylene oxide having a number average molecular weight of 1,000 to 3,000, and epichlorohydrin. The reaction causes a modified polyphenylene oxide having a low molecular weight with an epoxy group introduced into the terminal.
【0008】本発明の請求項4に係るエポキシ樹脂組成
物は、エポキシ樹脂、請求項1乃至請求項3に係る製法
によって得られた変成ポリフェニレンオキサイド、及び
エポキシ樹脂の硬化剤を必須成分として含有し、金属箔
の引き剥がし強度、半田耐熱性、メッキ染み込み性並び
に高周波特性の指標である誘電率、誘電正接特性に優れ
た積層板の製造に有用なものである。The epoxy resin composition according to a fourth aspect of the present invention comprises an epoxy resin, a modified polyphenylene oxide obtained by the production method according to the first to third aspects, and a curing agent for the epoxy resin as essential components. It is useful for the production of a laminate having excellent peeling strength of metal foil, solder heat resistance, plating penetration, and dielectric constant and dielectric loss tangent which are indicators of high frequency characteristics.
【0009】本発明の請求項5に係るプリプレグは、請
求項4のエポキシ樹脂組成物を基材に含浸し、このエポ
キシ樹脂組成物中のエポキシ樹脂とエポキシ変成ポリフ
ェニレンオキサイドがエポキシ樹脂の硬化剤によりBス
テージに半硬化したもので、金属箔の引き剥がし強度、
半田耐熱性、メッキ染み込み性並びに高周波特性の指標
である誘電率、誘電正接特性に優れた積層板の製造に有
用なものである。According to a fifth aspect of the present invention, there is provided a prepreg wherein a substrate is impregnated with the epoxy resin composition of the fourth aspect, and the epoxy resin and the epoxy-modified polyphenylene oxide in the epoxy resin composition are cured by a curing agent for the epoxy resin. It is semi-cured on the B stage, and has a metal foil peeling strength.
It is useful in the production of a laminate having excellent solder heat resistance, plating penetration, and a dielectric constant and a dielectric loss tangent characteristic which are indicators of high frequency characteristics.
【0010】本発明の請求項6に係る積層板は、請求項
5のプリプレグを加熱加圧したもので、プリプレグ中の
半硬化したエポキシ樹脂の硬化が完結すると、エポキシ
樹脂の硬化物の架橋構造にポリフェニレンオキサイドが
関与し、その結果、金属箔の引き剥がし強度、半田耐熱
性、メッキ染み込み性並びに高周波特性の指標である誘
電率、誘電正接特性に優れたものである。A laminate according to a sixth aspect of the present invention is obtained by heating and pressing the prepreg of the fifth aspect. When the curing of the semi-cured epoxy resin in the prepreg is completed, the crosslinked structure of the cured epoxy resin is completed. And polyphenylene oxide. As a result, the metal foil is excellent in peel strength, solder heat resistance, plating penetration property, and dielectric constant and dielectric loss tangent which are indicators of high frequency characteristics.
【0011】以下、本発明の実施形態を詳述する。Hereinafter, embodiments of the present invention will be described in detail.
【0012】[0012]
【発明の実施の形態】本発明の製法によって生成される
変成ポリフェニレンオキサイドは、末端にエポキシ基が
導入された変成PPOである。この変成PPOは、エポ
キシ樹脂の硬化物の架橋構造に関与するもので、数平均
分子量が10000乃至30000の高分子PPOをフ
ェノール性化合物と高分子PPOのラジカル開始剤の存
在下で再分配反応させることによって末端にフェノール
性化合物のフェノール性水酸基を有する低分子のフェノ
ール変成PPOを原料とし、このフェノール変成PPO
は数平均分子量が1000〜3000に制限される。す
なわち、フェノール変成PPOの数平均分子量が100
0未満では積層板の耐熱性が低下し3000を越える
と、基材に含浸したエポキシ樹脂のBステージに変成し
た半硬化物の溶融粘度が増大し、その結果積層板の金属
箔の引き剥がし強度、半田耐熱性、メッキ染み込み性の
性能を阻害するからである。BEST MODE FOR CARRYING OUT THE INVENTION The modified polyphenylene oxide produced by the production method of the present invention is a modified PPO having an epoxy group introduced into a terminal. The modified PPO is involved in the crosslinked structure of the cured epoxy resin, and causes a redistribution reaction of a high-molecular PPO having a number average molecular weight of 10,000 to 30,000 in the presence of a phenolic compound and a radical initiator of the high-molecular PPO. Thus, a low-molecular-weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at a terminal is used as a raw material,
Is limited to a number average molecular weight of 1,000 to 3,000. That is, the number average molecular weight of the phenol-modified PPO is 100
If the value is less than 0, the heat resistance of the laminate decreases, and if it exceeds 3000, the melt viscosity of the semi-cured product of the epoxy resin impregnated in the base material transformed into the B stage increases, and as a result, the peel strength of the metal foil of the laminate is increased. This is because they impair the performance of solder heat resistance and plating penetration.
【0013】上記の高分子PPOとしては、代表的な一
例を示すとポリ(2,6−ジメチル−1,4フェニレン
オキサイド)を挙げることができる。このような高分子
PPOは、たとえばUSP4,059,568号の明細
書に開示された合成法により製造することができる。A typical example of the above-mentioned polymer PPO is poly (2,6-dimethyl-1,4-phenylene oxide). Such a polymer PPO can be produced, for example, by a synthesis method disclosed in the specification of US Pat. No. 4,059,568.
【0014】この高分子PPOの再分配反応に用いられ
るフェノール性化合物としては、ポリフェノールのビス
フェノールA、フェノ−ルノボラック、クレゾールノボ
ラック等、フェノール性水酸基を分子内に2個以上有す
る多官能のフェノール類が好ましい。ラジカル開始剤と
しては、ジクミルパーオキサイド、tert−ブチルク
ミルパーオキサイド、ジ−tert−ブチルパーオキサ
イド、2・5−ジメチル−2・5−ジ−tert−ブチ
ルパーオキシヘキシン3、2・5−ジメチル−2・5−
ジ−tert−ブチルパーオキシヘキサン、α・α’−
ビス(tert−ブチルパーオキシ−m−イソプロピ
ル)ベンゼン〔1・4(または1・3)−ビス(ter
t−ブチルパーオキシイソプロピル)ベンゼンともい
う〕、ベンゾイルパーオキサイド(以下、BPOと記
す)などの過酸化物を挙げることができる。また、開始
剤として過酸化物ではないが、市販の開始剤である日本
油脂(株)製の商品名「ビスクミル」(1分半減温度3
30℃)を使用することもできる。Examples of the phenolic compound used in the redistribution reaction of the high-molecular PPO include polyfunctional phenols having two or more phenolic hydroxyl groups in the molecule, such as polyphenols such as bisphenol A, phenol-novolak and cresol novolak. preferable. Examples of the radical initiator include dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne 3, 2.5. -Dimethyl-2-2.5-
Di-tert-butylperoxyhexane, α · α′-
Bis (tert-butylperoxy-m-isopropyl) benzene [1.4 (or 1.3) -bis (ter
t-butylperoxyisopropyl) benzene] and benzoyl peroxide (hereinafter referred to as BPO). Although not a peroxide as an initiator, it is a commercially available initiator manufactured by Nippon Oil & Fats Co., Ltd. under the trade name “Biscumyl” (1 minute half-life temperature 3
30 ° C.) can also be used.
【0015】ラジカル開始剤の存在下で数平均分子量が
10000乃至30000の高分子PPOとフェノール
性化合物をトルエン、クロロホルム等の溶媒中で反応さ
せると、先ず高分子PPOがラジカル化され、直鎖が切
断された低分子のPPOが生成する再分配反応が進行
し、この活性化された低分子PPOとフェノール性化合
物とが反応して末端にフェノール性化合物のフェノール
性水酸基を有する低分子のフェノール変成PPOが生成
する。When a polymer PPO having a number average molecular weight of 10,000 to 30,000 and a phenolic compound are reacted in a solvent such as toluene or chloroform in the presence of a radical initiator, first, the polymer PPO is radicalized to form a linear chain. A redistribution reaction in which a cut low-molecular-weight PPO is generated proceeds, and the activated low-molecular-weight PPO reacts with a phenolic compound to convert a low-molecular-weight phenol having a phenolic hydroxyl group of a phenolic compound at a terminal. A PPO is generated.
【0016】なお、ベンゾイルパーオキサイドの量は、
ポリフェニレンエーテル100重量部に対して3〜10
重量部で、フェノール性化合物の量は3〜20重量部が
適量である。すなわち、ベンゾイルパーオキサイドなら
びにフェノール性化合物の添加量が過剰になると、再分
配反応が過度に進行し低分子のポリフェニレンオキサイ
ドの数平均分子量が低下し、その結果前述の如く耐熱性
が低下する。また、少な過ぎると再分配反応が進行せず
数平均分子量の低下が起こらない。The amount of benzoyl peroxide is as follows:
3 to 10 based on 100 parts by weight of polyphenylene ether
The appropriate amount of the phenolic compound is 3 to 20 parts by weight. That is, when the amounts of the benzoyl peroxide and the phenolic compound are excessively increased, the redistribution reaction proceeds excessively, and the number average molecular weight of the low molecular weight polyphenylene oxide decreases. As a result, the heat resistance decreases as described above. On the other hand, if the amount is too small, the redistribution reaction does not proceed and the number average molecular weight does not decrease.
【0017】再分配反応はトルエン、ベンゼン、キシレ
ン等の芳香族炭化水素系溶媒中で80〜120℃に10
〜100分加熱して行う。この再分配反応を通して、末
端にフェノール性化合物のフェノール性水酸基を有する
低分子のフェノール変成PPOが生成する。The redistribution reaction is carried out at 80 to 120 ° C. in an aromatic hydrocarbon solvent such as toluene, benzene or xylene.
Heat for ~ 100 minutes. Through this redistribution reaction, a low-molecular-weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at its terminal is produced.
【0018】次に本発明の変性ポリフェニレンオキサイ
ドを生成する、低分子PPOから成るフェノール変成P
POとエピクロルヒドリンとの反応について説明する。Next, a phenol-modified P composed of a low-molecular-weight PPO to form the modified polyphenylene oxide of the present invention.
The reaction between PO and epichlorohydrin will be described.
【0019】フェノール変成PPOの末端に導入された
フェノール性水酸基と反応してエポキシ化するエピクロ
ルヒドリンのモル数は、末端のフェノール性水酸基に対
して1倍以上好ましくは2倍以上の割合で使用し、反応
条件は80〜120℃で1〜10時間が好ましい。この
反応には、水酸化ナトリウム、水酸化カリウム等のアル
カリ金属の水酸化物の水溶液が有効で、エピクロルヒド
リンのエポキシ基に対して1当量以上好ましくは1.2
当量以上特に好ましくは1.5当量以上使用する。この
反応には、前述のPPOの再分配反応の際に用いた溶媒
を引き続き使用してもよく、他の溶媒に切り換えてもよ
い。反応後は、系を冷却しメタノールの如きPPOに対
して貧溶媒に生成物を注ぎ込み沈殿として析出させ、さ
らにこの沈殿物を濾過して分離し、水又はメタノールで
洗浄し、未反応のエピクロルヒドリンや前記の触媒を除
去した後50〜80℃で減圧乾燥して、目的とする本発
明の変成ポリフェニレンオキサイドを高い純度で得るこ
とができる。The number of moles of epichlorohydrin to be epoxidized by reacting with the phenolic hydroxyl group introduced into the terminal of the phenol-modified PPO is at least 1 times, preferably at least 2 times the ratio of the terminal phenolic hydroxyl group, The reaction conditions are preferably at 80 to 120 ° C for 1 to 10 hours. For this reaction, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is effective, and at least 1 equivalent, preferably 1.2 equivalent, to the epoxy group of epichlorohydrin.
It is used in an amount of at least equivalent, particularly preferably at least 1.5 equivalent. In this reaction, the solvent used in the above-described redistribution of PPO may be continuously used, or may be switched to another solvent. After the reaction, the system is cooled and the product is poured into a poor solvent for PPO such as methanol to precipitate as a precipitate. The precipitate is separated by filtration, washed with water or methanol, and unreacted epichlorohydrin or After removing the catalyst, the catalyst is dried under reduced pressure at 50 to 80 ° C. to obtain the desired modified polyphenylene oxide of the present invention with high purity.
【0020】このようにして得られた本発明の変成ポリ
フェニレンオキサイドは、溶融粘度が低く流動性に富
み、ビスフェノ−ルA型エポキシ樹脂、ビスフェノ−ル
F型エポキシ樹脂、ビスフェノ−ルS型エポキシ樹脂、
フェノ−ルノボラック型エポキシ樹脂、クレゾールノボ
ラック型エポキシ樹脂、イソシアヌレート型エポキシ樹
脂、ヒダントイン型エポキシ樹脂、脂環式エポキシ樹
脂、ビフェニル型エポキシ樹脂、及び、多官能エポキシ
樹脂等のエポキシ樹脂にも相溶性に富み、均質なワニス
を構成するエポキシ樹脂組成物を与える。The modified polyphenylene oxide of the present invention thus obtained has a low melt viscosity and a high fluidity, and contains bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin. ,
Compatible with epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, isocyanurate type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin and polyfunctional epoxy resin Provides an epoxy resin composition that constitutes a rich, homogeneous varnish.
【0021】なお、本発明の変成ポリフェニレンオキサ
イドは、ポリアミンやポリカルボン酸化合物を反応させ
て末端アミンPPOや末端カルボン酸PPOを製造する
原料としても有用である。The modified polyphenylene oxide of the present invention is also useful as a raw material for producing a terminal amine PPO or a terminal carboxylic acid PPO by reacting a polyamine or a polycarboxylic acid compound.
【0022】次に基材に含浸するワニスの形態で使用さ
れる、本発明のエポキシ樹脂組成物について説明する。
このエポキシ樹脂組成物は、エポキシ樹脂、上記の変成
ポリフェニレンオキサイド、及びエポキシ樹脂の硬化剤
を必須成分として含有して成るもので、上記の変成ポリ
フェニレンオキサイドは末端にエポキシ基を有する樹脂
であるからして、この樹脂とは別に配合される上記エポ
キシ樹脂とともにエポキシ樹脂成分として作用する。こ
こで、エポキシ樹脂組成物の主要成分である上記エポキ
シ樹脂としては、積層板に使用されるエポキシ樹脂であ
れば特に限定されるものではなく、例えば、ビスフェノ
−ルA型エポキシ樹脂、ビスフェノ−ルF型エポキシ樹
脂、ビスフェノ−ルS型エポキシ樹脂、フェノ−ルノボ
ラック型エポキシ樹脂、クレゾールノボラック型エポキ
シ樹脂、イソシアヌレート型エポキシ樹脂、ヒダントイ
ン型エポキシ樹脂、脂環式エポキシ樹脂、ビフェニル型
エポキシ樹脂、及び、多官能エポキシ樹脂等が挙げら
れ、これらの単独あるいは混合して使用される。さら
に、これらの樹脂を臭素化した難燃化エポキシ樹脂も使
用することができる。Next, the epoxy resin composition of the present invention used in the form of a varnish for impregnating a substrate will be described.
This epoxy resin composition contains an epoxy resin, the above-mentioned modified polyphenylene oxide, and a curing agent for the epoxy resin as essential components. The modified polyphenylene oxide is a resin having an epoxy group at a terminal. Thus, it acts as an epoxy resin component together with the above-mentioned epoxy resin compounded separately from this resin. Here, the epoxy resin, which is a main component of the epoxy resin composition, is not particularly limited as long as it is an epoxy resin used for a laminated board. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, isocyanurate type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, and Examples thereof include polyfunctional epoxy resins, and these are used alone or in combination. Further, flame-retardant epoxy resins obtained by brominating these resins can also be used.
【0023】これらのエポキシ樹脂の硬化剤としては、
通常使用される第一級、第2級アミン等のアミン系、ビ
スフェノールA、ビスフェノールF等のポリフェノール
を含むフェノール系、酸無水物系を挙げることができ
る。これらは、単独あるいは複数混合して使用される。As a curing agent for these epoxy resins,
Examples thereof include commonly used amines such as primary and secondary amines, phenols containing polyphenols such as bisphenol A and bisphenol F, and acid anhydrides. These may be used alone or in combination.
【0024】また、エポキシ樹脂の硬化反応には、必要
に応じて例えばイミダゾール系の硬化促進剤、その他通
常使用される促進剤が添加される。For the curing reaction of the epoxy resin, if necessary, for example, an imidazole-based curing accelerator and other commonly used accelerators are added.
【0025】ここで、エポキシ樹脂組成物の硬化機構に
ついて言及すると、エポキシ基を導入した変成PPOは
硬化剤によって主要成分のエポキシ樹脂とも結合する。
したがって、変成PPOはエポキシ樹脂の架橋構造に架
橋構造に関与することになる。Here, referring to the curing mechanism of the epoxy resin composition, the modified PPO into which the epoxy group has been introduced is also bound to the main component epoxy resin by the curing agent.
Therefore, the modified PPO participates in the crosslinked structure of the epoxy resin.
【0026】上記のエポキシ樹脂組成物をワニスの形態
でガラス布、ガラス不織布等に含浸乾燥して得られたプ
リプレグは、金属箔の引き剥がし強度、半田耐熱性、メ
ッキ染み込み性並びに高周波特性の指標である誘電率、
誘電正接特性に優れた積層板を与える。The prepreg obtained by impregnating the above-mentioned epoxy resin composition in the form of a varnish into a glass cloth, a glass non-woven fabric or the like is used as an indicator of the peel strength of metal foil, solder heat resistance, plating penetration and high frequency characteristics. Dielectric constant,
A laminate having excellent dielectric loss tangent characteristics is provided.
【0027】このプリプレグは、以下のような方法でつ
くることができる。ワニス中に基材を浸漬するなどし
て、基材にこれらの樹脂ワニスを含浸させ付着させる。
プリプレグの樹脂含有量は、特に限定しないが、30〜
70重量%とするのが好ましい。また、含浸時には、樹
脂ワニスを25〜35℃に保つと樹脂ワニス中のエポキ
シ樹脂に対する硬化剤の硬化反応を阻止し、基材への含
浸性を高めることができ、積層板の特性を良好にするこ
とができる。樹脂ワニスを含浸後加熱乾燥するに当たっ
ては、80〜180℃の温度が好ましい。その理由は、
この加熱乾燥が不十分であると、プリプレグ表面部分の
みの乾燥に止まり溶媒が内部に残留する為にプリプレグ
の表面と内部との間で樹脂の濃度差に起因する歪が生
じ、プリプレグ表面に微細なクラックが発生する。ま
た、過度に加熱乾燥をすると、プリプレグ表面では乾燥
過程で急激な粘度変化が起こるためにプリプレグ表面に
スジムラや樹脂タレが発生し、金属箔とプリプレグとの
密着性にムラが生じ、その結果金属箔の引き剥がし強
さ、半田耐熱性、誘電特性に大小、強弱のムラが発生す
る。This prepreg can be made by the following method. The substrate is impregnated with these resin varnishes by, for example, immersing the substrate in a varnish.
The resin content of the prepreg is not particularly limited.
Preferably it is 70% by weight. In addition, at the time of impregnation, if the resin varnish is kept at 25 to 35 ° C., the curing reaction of the curing agent with respect to the epoxy resin in the resin varnish can be prevented, and the impregnation property to the base material can be increased, and the characteristics of the laminate can be improved can do. In heating and drying after impregnating the resin varnish, a temperature of 80 to 180 ° C is preferable. The reason is,
If the heating and drying is insufficient, only the surface of the prepreg stops drying, and the solvent remains inside, causing distortion due to the difference in the concentration of the resin between the surface and the inside of the prepreg. Cracks occur. Also, if the prepreg surface is excessively heated and dried, the viscosity of the prepreg surface changes rapidly during the drying process, causing uneven streaks and resin sagging on the prepreg surface, resulting in uneven adhesion between the metal foil and the prepreg. Large and small unevenness in the peeling strength of the foil, the heat resistance of the solder, and the dielectric properties occur.
【0028】なお、基材としては、ガラスクロス、アラ
ミドクロス、ポリエステルクロス、パルプ紙、リンター
紙等が挙げられる。Examples of the substrate include glass cloth, aramid cloth, polyester cloth, pulp paper, linter paper and the like.
【0029】次に本発明の積層板について説明する。上
記のプリプレグの数枚と要すれば金属箔を積層して被圧
体とし、この被圧体を加熱加圧して積層板を得る。金属
箔としては、銅箔、アルミニューム箔等が用いられる。
加圧は、金属箔およびシートの接合と、厚みの調整のた
めに行うので、加圧条件は必要に応じて選択することが
できる。また、変成ポリフェニレンオキサイドとエポキ
シ樹脂とこれらののエポキシ樹脂の硬化剤の架橋反応
は、主として硬化剤の反応特性に依存するので、硬化剤
の種類に応じて加熱温度、加熱時間を選ぶ。たとえば、
一般には温度150〜300℃、圧力50kg/c
m2 、時間10〜60分程度が目安である。Next, the laminate of the present invention will be described. If several of the above prepregs are required, metal foils are laminated to form a pressed body, and the pressed body is heated and pressed to obtain a laminated plate. As the metal foil, a copper foil, an aluminum foil or the like is used.
Pressing is performed for joining the metal foil and sheet and adjusting the thickness, so that the pressing conditions can be selected as necessary. Further, since the crosslinking reaction between the modified polyphenylene oxide, the epoxy resin, and the curing agent of these epoxy resins mainly depends on the reaction characteristics of the curing agent, the heating temperature and heating time are selected according to the type of the curing agent. For example,
Generally, temperature 150-300 ° C, pressure 50kg / c
The standard is about m 2 and the time is about 10 to 60 minutes.
【0030】このようにして得られた金属箔張り積層板
は、エポキシ樹脂とポリフェニレンオキサイドの特性が
損なわれず、誘電特性等の高周波特性が優れ、しかも半
田耐熱性を左右する耐熱性、接着強度の強弱に起因する
スルホール、パンチング等の加工性、メッキ液の染み込
みの信頼性も優れたものとなる。The metal foil-clad laminate thus obtained does not impair the properties of the epoxy resin and the polyphenylene oxide, has excellent high-frequency properties such as dielectric properties, and has heat resistance and adhesive strength that affect solder heat resistance. The processability such as through holes and punching due to the strength and the reliability of the penetration of the plating solution are also excellent.
【0031】なお、本発明のエポキシ樹脂組成物は、溶
媒を介して樹脂ワニスとし、この樹脂ワニスをガラスク
ロス等の基材に含浸乾燥してプリプレグとしての使用例
に限るものではなく、たとえばキャスチィング法により
基材を含まないシートを作成し、このシートをプリプレ
グに代用することもできる。このキャステング法に依る
ときは、例えばワニスをワニスの溶媒に不溶のポリエス
テルフィルム、ポリイミドフィルムなどの離型シートに
5〜700μmの厚みに塗布し、十分に乾燥させると、
ブレンドした樹脂を熱溶融する押出成形によるのと比較
すると比較的低温でより容易にシ−卜を造ることができ
る点で優れている。ワニスをキャステングする前記シー
トは、離型剤で表面処理したシートを用いると剥離が容
易になるので実際的である。The epoxy resin composition of the present invention is not limited to an example of use as a prepreg by forming a resin varnish through a solvent, impregnating the resin varnish into a substrate such as a glass cloth and drying the resin varnish. A sheet containing no base material can be prepared by the method, and this sheet can be used as a prepreg. When using this casting method, for example, a varnish is applied to a release sheet such as a polyester film or a polyimide film insoluble in a solvent for the varnish to a thickness of 5 to 700 μm and dried sufficiently.
Compared with the extrusion molding in which the blended resin is melted by heat, it is excellent in that a sheet can be easily produced at a relatively low temperature. The varnish-casting sheet is practical because the use of a sheet surface-treated with a release agent facilitates peeling.
【0032】以下、本発明の実施形態を実施例によって
具体的に説明する。Hereinafter, embodiments of the present invention will be specifically described with reference to examples.
【0033】[0033]
(実施例1)先ず、数平均分子量Mn=20000の高
分子PPO(日本G.E.プラスチック(株)製)10
0重量部(以下、部と記す)、ベンゾイルパーオキサイ
ド6部、及びフェノール性化合物のビスフェノ−ルA6
部にトルエン100部を添加し90℃にて60分間攪拌
し、再分配反応させて末端にフェノール性化合物のフェ
ノール性水酸基を有する低分子のフェノール変性PPO
の溶液を得た。この溶液をゲル浸透クロマトグラフ(カ
ラム構成:東ソー(株)製 SuperHM-M(1本)+SuperH
M −H (1本))にて分子量分布を測定した結果、数平
均分子量は2300であった。(Example 1) First, a polymer PPO having a number average molecular weight Mn = 20,000 (manufactured by GE Plastics Japan) 10
0 parts by weight (hereinafter referred to as "parts"), 6 parts of benzoyl peroxide, and bisphenol A6 of a phenolic compound
100 parts of toluene was added thereto, and the mixture was stirred at 90 ° C. for 60 minutes, and subjected to a redistribution reaction to obtain a low-molecular-weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at its terminal.
Was obtained. This solution was subjected to gel permeation chromatography (column composition: SuperHM-M (1) from Tosoh Corporation) + SuperH
As a result of measuring the molecular weight distribution by M-H (1 line), the number average molecular weight was 2,300.
【0034】次に、この溶液210部にエピクロルヒド
リン8部と水酸化ナトリューム水溶液(50%)8部を
加えて100℃で4時間攪拌した後に室温まで冷却しメ
タノール1リットルを加えて末端にエポキシ基を導入し
た変性PPOを沈殿させた。この沈殿物を濾別し、メタ
ノール1リットルと水1リットルで2回洗浄し、最後に
メタノール1リットルで洗浄し、70℃で減圧乾燥し、
変成ポリフェニレンオキサイド(変成PPO(A))を
精製した。Next, 8 parts of epichlorohydrin and 8 parts of an aqueous sodium hydroxide solution (50%) were added to 210 parts of this solution, stirred at 100 ° C. for 4 hours, cooled to room temperature, and 1 liter of methanol was added. Was introduced to precipitate the denatured PPO. The precipitate was separated by filtration, washed twice with 1 liter of methanol and 1 liter of water, finally, washed with 1 liter of methanol, and dried at 70 ° C. under reduced pressure.
The modified polyphenylene oxide (modified PPO (A)) was purified.
【0035】フェノール変成PPOとエピクロルヒドリ
ンとの反応率は91%であった。この反応率は、PPO
の1.5重量%の四塩化炭素溶液を光路長10mmの石
英セルを用いて赤外線スペクトルを測定し、反応前後の
フェノール性水酸基の吸光度(3622cm-1)の値に
より求めた。The conversion between the phenol-modified PPO and epichlorohydrin was 91%. This reaction rate is
The 1.5% by weight of the carbon tetrachloride solution was measured for its infrared spectrum using a quartz cell having an optical path length of 10 mm, and the absorbance of the phenolic hydroxyl group before and after the reaction (3622 cm -1 ) was determined.
【0036】(実施例2乃至実施例3)実施例1で得た
フェノール変成PPOの溶液を用い、(表1)に示す配
合に基づき実施例1と同一の条件でエピクロルヒドリン
を反応させ、エポキシ基を導入した本発明の変性ポリフ
ェニレンオキサイド(変成PPO(B))、(変成PP
O(C)を得た。(Examples 2 and 3) Using the phenol-modified PPO solution obtained in Example 1 and reacting epichlorohydrin under the same conditions as in Example 1 based on the composition shown in Table 1, the epoxy group was added. Modified polyphenylene oxide of the present invention (modified PPO (B)), (modified PP
O (C) was obtained.
【0037】(実施例4)実施例1で用いた高分子PP
O100部、ベンゾイルパーオキサイド4部、及びフェ
ノール性化合物のビスフェノ−ルA4部にトルエン10
0部を添加し、実施例1と同一の反応条件で再分配反応
させて末端にフェノール性化合物のフェノール性水酸基
を有する低分子のフェノール変性PPOの溶液を得た。
数平均分子量は2800であった。Example 4 Polymer PP used in Example 1
To 100 parts of O, 4 parts of benzoyl peroxide, and 4 parts of bisphenol A of a phenolic compound, toluene 10
0 parts were added and redistributed under the same reaction conditions as in Example 1 to obtain a solution of a low-molecular-weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at the terminal.
The number average molecular weight was 2,800.
【0038】次に、この溶液210部にエピクロルヒド
リン4部と水酸化ナトリューム水溶液(50%)24部
を加えて実施例1と同一の条件で反応させて末端にエポ
キシ基を導入した変性PPOを沈殿させた。この沈殿物
を濾別し、メタノール1リットルと水1リットルで2回
洗浄し、最後にメタノール1リットルで洗浄し、70℃
で減圧乾燥し、変成ポリフェニレンオキサイド(変成P
PO(D))を精製した。Next, 4 parts of epichlorohydrin and 24 parts of an aqueous sodium hydroxide solution (50%) were added to 210 parts of this solution and reacted under the same conditions as in Example 1 to precipitate denatured PPO having an epoxy group introduced into the terminal. I let it. This precipitate was separated by filtration, washed twice with 1 liter of methanol and 1 liter of water, and finally washed with 1 liter of methanol.
And dried under reduced pressure, using modified polyphenylene oxide (modified P
PO (D)) was purified.
【0039】(実施例5)実施例1で用いた高分子PP
O100部、ベンゾイルパーオキサイド10部、及びフ
ェノール性化合物のビスフェノ−ルA10部にトルエン
100部を添加し、実施例1と同一の反応条件で再分配
反応させて末端にフェノール性化合物のフェノール性水
酸基を有する低分子のフェノール変性PPOの溶液を得
た。数平均分子量は1300であった。Example 5 Polymer PP used in Example 1
To 100 parts of O, 10 parts of benzoyl peroxide, and 10 parts of bisphenol A of a phenolic compound, 100 parts of toluene was added, and redistribution reaction was carried out under the same reaction conditions as in Example 1 to terminate the phenolic hydroxyl group of the phenolic compound. A solution of a low molecular weight phenol-modified PPO having the following formula: The number average molecular weight was 1,300.
【0040】次に、この溶液210部にエピクロルヒド
リン24部と水酸化ナトリューム水溶液(50%)24
部を加えて実施例1と同一の条件で反応させて末端にエ
ポキシ基を導入した変性PPOを沈殿させた。この沈殿
物を濾別し、メタノール1リットルと水1リットルで2
回洗浄し、最後にメタノール1リットルで洗浄し、70
℃で減圧乾燥し、変成ポリフェニレンオキサイド(変成
PPO(E))を精製した。Next, 24 parts of epichlorohydrin and 24 parts of sodium hydroxide aqueous solution (50%) were added to 210 parts of this solution.
The modified PPO having an epoxy group introduced at the terminal was precipitated by adding the same and reacting under the same conditions as in Example 1. The precipitate was filtered off and washed with 1 liter of methanol and 1 liter of water.
Wash twice, and finally with 1 liter of methanol, 70
After drying under reduced pressure at ℃, modified polyphenylene oxide (modified PPO (E)) was purified.
【0041】(表1)に実施例1乃至実施例5の変成P
PO(A)、(B)、(C)、(D)、(E)を製造し
たPPO、エピクロルヒドリン、水酸化ナトリウムの配
合比率を示した。(Table 1) shows the modified P of Examples 1 to 5.
The mixing ratios of PPO, epichlorohydrin, and sodium hydroxide that produced PO (A), (B), (C), (D), and (E) are shown.
【0042】(実施例6〜実施例10)実施例1乃至実
施例5で得た変成PPO(A)、(B)、(C)を用い
て (表2)に示した成分の配合割合に従いセパラブル
フラスコに入れ、室温で30分間攪拌し空冷を行い25
℃のワニスを得た。このワニスは初期の粘度も小さく、
析出現象もなく保存性に優れていた。24時間後に樹脂
ワニスを0.1mmのEガラスクロスに含浸し、140
℃で4分間乾燥し、樹脂含有率53重量%のプリプレグ
を得た。このプリプレグは、(表3)に示す如く、表面
が平滑で樹脂の含浸ムラもなく、このワニスの良好な含
浸性を裏付けるものであった。(Examples 6 to 10) Using the modified PPOs (A), (B) and (C) obtained in Examples 1 to 5, according to the mixing ratios of the components shown in Table 2 Place in a separable flask, stir at room temperature for 30 minutes, air-cool,
° C varnish was obtained. This varnish also has a low initial viscosity,
There was no precipitation phenomenon and the storage stability was excellent. After 24 hours, a 0.1 mm E glass cloth was impregnated with a resin varnish,
Drying at 4 ° C. for 4 minutes gave a prepreg having a resin content of 53% by weight. As shown in (Table 3), this prepreg had a smooth surface and no unevenness in impregnation of the resin, and supported the good impregnation of the varnish.
【0043】このプリプレグに対して外観、取扱性、含
浸性について評価した結果を(表3)に示した。The results of evaluating the appearance, handleability and impregnation of the prepreg are shown in Table 3.
【0044】次に、このプリプレグを8枚重ね合わせ、
その両面に18μmの銅箔を配置して被圧体とし、19
0℃で圧力20kg/cm2 で100分加熱加圧し両面
に銅箔が積層された銅張り積層板を得た。この積層板に
ついて銅箔引き剥し強さ、PCT半田耐熱性、誘電率、
及び誘電正接を測定し、測定結果を(表3)に示した。
なお、誘電率、及び誘電正接はMILに規定する測定条
件によった。Next, eight prepregs are superimposed,
A copper foil of 18 μm was arranged on both sides to form a pressure-receiving body.
Heating and pressing was performed at 0 ° C. and a pressure of 20 kg / cm 2 for 100 minutes to obtain a copper-clad laminate having copper foil laminated on both sides. The copper foil peeling strength, PCT solder heat resistance, dielectric constant,
And the dielectric loss tangent were measured, and the measurement results are shown in (Table 3).
Note that the dielectric constant and the dielectric loss tangent were based on measurement conditions specified in MIL.
【0045】[0045]
(比較例1)実施例1の高分子PPO101部、ベンゾ
イルパーオキサイド1部、及びフェノール性化合物のビ
スフェノ−ルA1部にトルエン100部を添加し90℃
にて60分間攪拌し、再分配反応させてフェノール変成
PPOの溶液を得た。このフェノール変性PPOの数平
均分子量は17000であった。(Comparative Example 1) To 100 parts of toluene was added to 101 parts of the polymer PPO of Example 1, 1 part of benzoyl peroxide, and 1 part of bisphenol A of a phenolic compound at 90 ° C.
For 60 minutes, and a redistribution reaction was performed to obtain a phenol-modified PPO solution. The number average molecular weight of this phenol-modified PPO was 17000.
【0046】次に、この溶液にエピクロルヒドリン2部
と水酸化ナトリューム水溶液(50%)2部を加え、実
施例1と同一の反応条件、処理条件で変性ポリフェニレ
ンオキサイド(変成PPO(F)を精製した。反応率は
92%であった。Next, 2 parts of epichlorohydrin and 2 parts of an aqueous sodium hydroxide solution (50%) were added to this solution, and the modified polyphenylene oxide (modified PPO (F) was purified under the same reaction conditions and processing conditions as in Example 1. The conversion was 92%.
【0047】(比較例2)実施例1の高分子PPO10
1部、ベンゾイルパーオキサイド30部、及びフェノー
ル性化合物のビスフェノ−ルA30部にトルエン100
部を添加し比較例1と同一の条件で再分配反応させてフ
ェノール変成PPOの溶液を得た。このフェノール変性
PPOの数平均分子量は700であった。Comparative Example 2 Polymer PPO10 of Example 1
1 part, 30 parts of benzoyl peroxide, and 30 parts of bisphenol A of phenolic compound
Was added and redistributed under the same conditions as in Comparative Example 1 to obtain a phenol-modified PPO solution. The number average molecular weight of this phenol-modified PPO was 700.
【0048】次に、この溶液にエピクロルヒドリン2部
と水酸化ナトリューム水溶液(50%)2部を加え、実
施例1と同一の反応条件、処理条件で変性ポリフェニレ
ンオキサイド(変成PPO(G)を精製した。Next, 2 parts of epichlorohydrin and 2 parts of an aqueous sodium hydroxide solution (50%) were added to this solution, and the modified polyphenylene oxide (modified PPO (G) was purified under the same reaction conditions and processing conditions as in Example 1. .
【0049】(比較例3)実施例1の高分子PPO10
1部、ベンゾイルパーオキサイド2部、及びフェノール
性化合物のビスフェノ−ルA2部にトルエン100部を
添加し比較例1と同一の条件で再分配反応させてフェノ
ール変成PPOの溶液を得た。このフェノール変性PP
Oの数平均分子量は3400であった。Comparative Example 3 Polymer PPO10 of Example 1
To 1 part, 2 parts of benzoyl peroxide and 2 parts of bisphenol A of a phenolic compound, 100 parts of toluene was added and redistributed under the same conditions as in Comparative Example 1 to obtain a phenol-modified PPO solution. This phenol-modified PP
The number average molecular weight of O was 3,400.
【0050】次に、この溶液にエピクロルヒドリン2部
と水酸化ナトリューム水溶液(50%)2部を加え、実
施例1と同一の反応条件、処理条件で変性ポリフェニレ
ンオキサイド(変成PPO(H)を精製した。Next, 2 parts of epichlorohydrin and 2 parts of an aqueous sodium hydroxide solution (50%) were added to this solution, and the modified polyphenylene oxide (modified PPO (H) was purified under the same reaction conditions and processing conditions as in Example 1. .
【0051】(比較例4乃至比較例6)比較例1乃至比
較例3の変成PPO(F)、(G)、(H)を用いて、
(表2)に示した成分の配合割合に従い実施例6乃至実
施例10と同一の条件でワニスを得た。このワニスを実
施例と同一のEガラスクロスに同一条件で含浸乾燥しプ
リプレグを得た。このプリプレグを用いて実施例と同一
の条件で銅張り積層板を得た。(Comparative Examples 4 to 6) Using the modified PPOs (F), (G) and (H) of Comparative Examples 1 to 3,
Varnishes were obtained under the same conditions as in Examples 6 to 10 according to the mixing ratios of the components shown in (Table 2). This varnish was impregnated and dried in the same E glass cloth as in the example under the same conditions to obtain a prepreg. Using this prepreg, a copper-clad laminate was obtained under the same conditions as in the example.
【0052】[0052]
【表1】 [Table 1]
【0053】[0053]
【表2】 [Table 2]
【0054】[0054]
【表3】 [Table 3]
【0055】実施例と比較例の樹脂ワニス特性、プリプ
レグ特性、積層板特性を対比すると、銅箔引き剥がし強
さ、半田耐熱性、メッキ染み込み性並びに高周波特性の
指標である誘電率、誘電正接特性に優れていることが明
白で、これは樹脂ワニスの含浸性が高まり、且つ本発明
の変成ポリフェニレンオキサイドがエポキシ樹脂の硬化
物を構成する架橋構造に関与していることによるもので
ある。Comparing the resin varnish characteristics, prepreg characteristics, and laminate characteristics of the examples and the comparative examples, the copper foil peeling strength, solder heat resistance, plating penetration property, and dielectric constant and dielectric loss tangent, which are indicators of high-frequency characteristics, are shown. It is apparent that the modified polyphenylene oxide of the present invention participates in the crosslinked structure constituting the cured product of the epoxy resin, because the impregnating property of the resin varnish is enhanced.
【0056】[0056]
【発明の効果】本発明によると、金属箔の引き剥し強
さ、半田耐熱性、メッキ染み込み性並びに高周波特性の
指標である誘電率、誘電正接特性に優れた積層板を与え
ることができる。According to the present invention, it is possible to provide a laminate excellent in the peeling strength of the metal foil, the solder heat resistance, the plating penetration property and the dielectric constant and the dielectric loss tangent characteristic which are indicators of the high frequency characteristics.
フロントページの続き (72)発明者 斎藤 英一郎 大阪府門真市大字門真1048番地松下電工 株式会社内 (56)参考文献 特開 平9−202851(JP,A) 特開 昭47−32097(JP,A) 特公 昭50−15519(JP,B1) (58)調査した分野(Int.Cl.7,DB名) C08G 65/00 - 65/48 Continuation of the front page (72) Inventor Eiichiro Saito 1048 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd. (56) References JP-A-9-202851 (JP, A) JP-A 47-32097 (JP, A) Japanese Patent Publication No. 50-15519 (JP, B1) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 65/00-65/48
Claims (6)
の高分子量のポリフェニレンオキサイドをポリフェノー
ル性化合物とラジカル開始剤の存在下で再分配反応させ
て得られた数平均分子量が1000〜3000のフェノ
ール変成ポリフェニレンオキサイド、及びエピクロルヒ
ドリンとを反応させることを特徴とする末端をエポキシ
化した変成ポリフェニレンオキサイドの製法。1. A compound having a number average molecular weight of 10,000 to 30,000
Reacting a high molecular weight polyphenylene oxide with a polyphenolic compound and a phenol-modified polyphenylene oxide having a number average molecular weight of 1,000 to 3,000 obtained by redistribution reaction in the presence of a radical initiator, and epichlorohydrin. A method for producing a modified polyphenylene oxide having epoxidized terminals.
キサイドである請求項1の変成ポリフェニレンオキサイ
ドの製法。2. The process for producing a modified polyphenylene oxide according to claim 1, wherein said radical initiator is benzoyl peroxide.
サイドにエピクロルヒドリンを反応させる際に触媒とし
てアルカリ金属の水酸化物を用いる請求項1又は請求項
2の変成ポリフェニレンオキサイドの製法。3. The process for producing a modified polyphenylene oxide according to claim 1, wherein an alkali metal hydroxide is used as a catalyst when reacting epichlorohydrin with the phenol-modified polyphenylene oxide.
いずれかの製法によって得られた変成ポリフェニレンオ
キサイド、及びエポキシ樹脂の硬化剤からなるエポキシ
樹脂組成物。4. An epoxy resin, according to claim 1, wherein
An epoxy resin composition comprising a modified polyphenylene oxide obtained by any one of the production methods and a curing agent for an epoxy resin.
たプリプレグ。5. A prepreg obtained by impregnating a substrate with the epoxy resin according to claim 4.
層板。6. A laminate obtained by heating and pressing the prepreg according to claim 5.
Priority Applications (1)
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JP12756696A JP3248424B2 (en) | 1996-02-29 | 1996-05-23 | Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg |
Applications Claiming Priority (3)
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---|---|---|---|
JP8-43045 | 1996-02-29 | ||
JP4304596 | 1996-02-29 | ||
JP12756696A JP3248424B2 (en) | 1996-02-29 | 1996-05-23 | Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg |
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JPH09291148A JPH09291148A (en) | 1997-11-11 |
JP3248424B2 true JP3248424B2 (en) | 2002-01-21 |
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ID=26382791
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-
1996
- 1996-05-23 JP JP12756696A patent/JP3248424B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2007097231A1 (en) | 2006-02-21 | 2007-08-30 | Asahi Kasei Chemicals Corporation | Process for producing low-molecular polyphenylene ether |
WO2007139172A1 (en) | 2006-05-25 | 2007-12-06 | Mitsubishi Gas Chemical Company, Inc. | Method for producing phenylene ether oligomer |
KR101208611B1 (en) | 2011-09-02 | 2012-12-06 | 도레이첨단소재 주식회사 | Adhesive composition containing epoxy terminated poly(alkylphenylene oxide)s and adhesion lead lock tape for semiconductor package using the same |
WO2013097128A1 (en) | 2011-12-29 | 2013-07-04 | 广东生益科技股份有限公司 | Method for preparing phosphorus-containing polyphenylene oxide resin with low molecular weight |
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